KINETICS AND MECHANISM OF THE REACTIONS BETWEEN ALKYL RADICALS AND COMPLEXES OF COBALT(III) AND RUTHENIUM(III)

The kinetics of the reactions of *C2H5 with cobalt(III) and ruthenium(III) complexes were studied by laser flash photolysis with ABTS*- as a kinetic probe. Some relative rate constants were also determined by a competition method based on product ratios. The substrates included a series of M(NH3)5X2+ complexes (= Co, Ru; X = halo, aquo, thiocyanate, azido) and some bis(dimethylglyoximato)halocobalt(III) complexes. The products of these reactions are largely (>90%) the ethyl halide and ethyl thiocyanate, substantiating an inner-sphere mechanism. Minor but regular yields of C2H4 are also found (≤10%), suggesting a small contribution from the outer-sphere oxidation of *C2K5. © 1990, American Chemical Society. All rights reserved.